Lubricating composition



. Anio'bject of the present duction ofia lubricating Patented May 20, 1947 ES PATENT OFF I LUBRICATING COMPOSITION Arnold J. Morway, Clark Township, Union County, and John C. Zimmer, Union, N. J.,

assignors to Standard Oil Development Company, a corporation of Delaware 2,420,902 ICE 1 No Drawing.) Application December 8, 1943,

; Serial-No. 513,475

7 Claims..

j-k oi. 252-36) The present invention relates to lubricating compositions and more particularly to lubricatin Y compositions especiallyadaptable for the lubrication yof the mechanical ;;parts -of, unde'r-water ficrafti 1 Mechanical Parts and mechanisms whichfare designed to operate in contact with watereither hydrocarbon-in which the halogen is substituted in the aromatic ring nucleus. Sucharomatic hydrocarbons may be represented by ben'zene, isointermittently ,or 1 continuously as when com- -pletely submerged and depending upon some ma-. terial or substance other than water for lubricatio'n present a very rtroublesomelubricating prob lem. Situations of this nature'arise inconnection jwith under-water" pumps 1 where the complete mechanism l remain'ssubmergedhr is intermit-' tentlyfin contact with-water, and in-the case of type ubri'ca'nts; becomes acute i -'Ihe external fmecha isms with which a submarine is equipped. such"asoonning tower hatch hinges, torpedo tubeportsii-periscope elevatingmechanis n' and more 1 recentlygun carriage as wellasfvarious internal mechanisms must -,be lubricated. .A lubricantflfor 'any-1 of1these purposes 'should be firstfwater-insoluble orsubstantiallywater insoluble Second I ly,"such a-lubricant shouldfhave a'density greater ater craftoperation the need for special cants have been proposed for use in contact with water, buttheir use has not'been completely satisf factory, particularly; inf-connection" with submarine operation. Prior-lubricants, being lighter] r v 1' thanflwater, tend tobe washed away-andfloat to the surface; Also thelubricants used within the. submersible tend to find theirfway intovthe bilge"- .water, due to leaks "around, bearings"'and"othercauses, where theyffloat; When-the bilge water is pumped out these waste andl'used lubricants float to the surface causing Yoilsli'bks-and wakes.

. These slicks and wakes arean almostcertain indication of the presence offsubmersibles,are readily seen by .observers-omsurface or airborne craft, thereby .makin'g theete'ction of under water craft relatively simple;

bricantsIwhere lnflammable naterlal which might 1 be ignited by' awspark' of}electricahmechanical orfchemical origin would 'be'a hazard. These and other objects" w ll be apparent'to those skilled in invention is the. propropyl benzene, naphthalene, dlphenyl, triphenyl, toluene, xylene and homologous derivativesthereof, and the halogenated products in general by the empirical formula (Halli Arom RM Ho, where Hal represents one of the halogens, chlorine, flu orine, bromine and iodine; Arom represents the benzene or naphthalene nucleus, R is hydrogen or'an alkyl radical such as methyl, ethyl, propyl,

isopropyl, etc., n and o are integers from 1-14 and m'isan integer from 1-3. Thefpreferred-halogenated aromatic hydrocarbons are solidsor oily liquids at ordinary temperatures having a density greater than 1.04; These halogenated aromatic vhydrocarbons can beproduced through the direct halogenation of the corresponding hydrocarbon h and by other knownxmeans and are relatively stable to hydrolysis. It is further preferred ."to

use those halogenated aromatic hydrocarbons containing from 20-60% 'of halogen on a weight basis; Solid halogenated aromatic hydrocarbonsv may be dissolved in liquid halogenated hydrocarbons to obtain'the required or desired density and fluidity. Compounds containing halogen substi-' tuted in an aliphatic or alkyl radical should not be used for the purposes of this invention for the "reason that compounds of this nature readily hydrolyze, yielding halogen acids; Specific examplesIof those halogenated aromatic hydrocarbons falling within the purview ofthe present inven- 2 ;tion are chloro-, bromo-, Or iodobenzene; chloro-, bromo-, iodoor fluorodiphenyl; methyl chlorobenzene, methyl dichlorobenzene; isopropyl trichlorobenzene, dimethylchlorobenzene, chloronaphthalene, etc. Unless specific steps are taken I to purify the product, halogenation of aromatic hydrocarbons results in a mixture of halogenated products, and for the purposes of the present in-,

vention, such a mixture need not be purified or further modified if it is of the proper density. It is intended that the lubricants of'the present inition which is. in-

vention shall contain from 95% of halogenated aromatichydrocarbons.

e; g the formation of the soaps utilized in the duction of the grease composition-of this invention; anysoap-stock, such as saturated or unsaturated-fats of either vegetable or animal'origin, sucli as stearin orcotton seed oil or. the saturated or"unsaturated fatty acid derived therethe art'upon reading thefollowing description.

, It'has now been discovered that lubricants sui tv ablefor under-water and non-inflamm-able;serv-'-,

ice can'l'bemade by employing a water-insoluble -frorn such as stearicacid or oleic acid may bev fused although it is preferred to use the saturated acids derived from hydrogenated fish oil. The soaps 'derived from the soap stocks must be water-insoluble, and for this purpose, neutraliz ing or saponifying agents are used, such as lith- 1 ium', calcium, bariun strontium, aluminum, zinc or leadj-which react with fatty acids to form water 'insoluble soaps, The preferred composi- Approximately 60% tions also include a bufiering agent, such as aluminum stearate for stabilizing the hydrogenion concentration, and an oxidation inhibitor such as zinc naphthenate, the zinc salt of a mono-carboxylic acid having more than six carbon atoms. a zinc phenate or a zinc salt of an alkylated phenol, phenol sulfide or thiophosphate. The amount of soap in the composition will vary somewhat ranging generally between 5 and 30% by weight, according to the consistency desired in the final product. Compositions containing from 51-10% of soap are semi-fluid products, while if 12 to 30% or more of soap is present, greases of firm structure increasing in consistency with rising soap content are obtained. The amount of buffer and oxidation inhibitor used will each range from about 0.1-1% by weight. The compositions herein described have no flash point and the spontaneous ignition point is above 1000 F.

In most instances, any of the methods customarily employed in the compounding of greases may be used in the production of the compositions of this invention, however, some halogenated hydrocarbons readily volatilize on heating, in which case the soaps may be produced separately-and then mixed with the halogenated hydrocarbon by heat and agitation. Where the soap is made separately the soap stock is first melted and then an aqueous solution or suspension of the alkaline material is added and the mixture is heated and stirred until the reaction is complete, after which the temperature is raised to boil off the water. The remainder of the materials may then be added and the temperature raised until a fluid grease is obtained which is generally in the range from 250-360 F. These compositions made in accordance with the foregoing description have been found to possess very marked characteristics in that they will not float in water and are water-insoluble.

The followingexamples will serve to illustrate the principles of the present invention.

Example 1 Per cent Hydrogenated fish oil acid 13.00 Lithium hydroxide monohydrate 2.05 Zinc naphthenate 0.50 Aluminum stearate 0.50

Chlorinated diphenyl containing 48% C1z 83.95

The hydrogenated fish oil acid and about 20% of the chlorinated diphenyl were charged to a kettle equipped with a stirrer, heating was started and when all the acid had melted the lithium hydroxide dissolved in as small an amount of bolling water as possible was added. After the soap was formed, heating was continued to around 200 F. until most of the water was removed. of the remainder of the chlorinated diphenyl was then added and the temperature raised to 300 F. A sample was then taken for alkalinity determination which should be from 0.1-0.2 figured as NaOH and the alkalinity of the batch was adjusted accordingly. The aluminum stearate, dispersed in the balance of the chlorinated diphenyl, was then added along with the zinc naphthenate to the kettle and the temperature was raised until the grease became fluid at about 360 F. Stirring and heating were then discontinued and the grease allowed to cool. After cooling the grease was worked to a smooth paste in the kettle and then filtered.

Chlorinated diphenyl containing 48% 012. 58.765

15 In compounding the composition of the example the hydrogenated fish oil acid and chlorinated diphenyl were heated together as described in Example 1, reacted with lithium hydroxide, heated to remove water after which the balance of the chlorinated diphenyl was added, the temperature raised to 300 F. and the batch adjusted for alkalinity. The aluminum stearate dispersed in the tri-chlor-benzene, together with the zinc naphthenate was then added to the kettie and the temperature was raised to the melting point of the grease. Stirring and heating were then discontinued and the grease allowed to cool after which the grease was worked to a smooth paste and filtered as described in Exampie 1. By operating in this manner, maximum control of the vapors of tri-chlor-benzene was obtained.

A. S. T. M. penetration, unworked 300 A. S. T. M. penetration, worked 305 Dropping point. F 352 What is claimed is:

1. A lubricating composition consisting of about 84% of an isomeric mixture of chlorinated diphenyl containing an average of 43% of ch10- rine. 15% lithium soap of hydrogenated fish oil acids, .5% aluminum stearate and .5% zinc naphthenate.

2. A lubricant comprising 5-30% of water- 45 insoluble metal soap wherein the metal of said soap is selected from the groupconsisting of lithium, calcium, barium, and strontium, 70-95% of an isomeric mixture of chlorinated diphenyl of 48% average chlorine content on a weight 50 basis, from 0.1 to 1% of aluminum stearate and from 0.1 to 1% of zinc naphthenate, said lubricant having a density greater than that of sea water.

3. A lubricating composition according to claim 2 in which the water-insoluble soap is a calcium soap.

4. A lubricating composition according to claim 2 in which the water-insoluble soap is a barium soap.

5. A lubricant comprising 5-30% of a water-insoluble metal soap wherein the metal of said soap is selected from the group consisting of lithium, calcium, barium, and strontium, about 25% of a halogenated aromatic hydrocarbon with a single benzene ring nucleus and approximately 60% of an isomeric mixture of chlorinated diphenyl of 48% average chlorine content on a weight basis, stabilized and buflered by 0.1 to 1 of aluminum stearate and 0.1 to 1% zinc naphthenate, the said lubricant having a density greater than that of sea water.

6. A lubricant comprising 5-30% of a waterinsoluble metal soap wherein the metal of said soap is selected from the group consisting of lithium, calcium, barium, and strontium, about 25% of a chlorinated aromatic hydrocarbon with a single benzene ring nucleus and. approximately 60% of an isomeric mixture of chlorinated diphenyl of 48% average chlorine content on a weight basis, stabilized and buffered by 0.1 to 1% of aluminum stearate and 0.1 to 1% of zinc naphthenate, said lubricant having a density greater than that of sea water.

7. A lubricant composition consisting of about 25% trichlorbenzene,--59% of an isomeric mixture of chlorinated diphenyl containing an aver- I age of 48% chlorine, 15% lithium soap of hy- REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,079,783 Wiezevich May 11, 1937 2,127,497 Webster Aug. 23, 1938 25 6 Number Name Date 2,274,674 EarIeI Mar. 3, 1942 2,283,602 Fiero May 19, 1942 2,293,052 Earle II Aug. 18, 1942 2,330,238 Prutton Sept. 28, 1943 2,332,825 Zimmer et a1. Oct. 26, 1943 2,354,171 Morgan July 18, 1944 2,360,631 Zimmer et al. Oct. 17, 1944 2,363,013 Morway et a1 Nov. 21, 1944 1,982,198 Brunstrum et al. Nov. 27, 1934 1,989,196 Hilliker et al. Jan. 29, 1935 2,245,772 Gothard et a1. June 17, 1941 2,383,148 Morgan et al. Aug. 21, 1945 OTHER REFERENCES Penning, Physical Characteristics and Commercial Possibilities of Chlorinated Diphenyl, Article in Industrial and Engineering Chemistry, vol. '22, pp. 1180, 1181, and 1182, Nov. 1930, 260-74.

Plasticizers and Resins, pub. by Monsanto Chemicals, revised May 1940, page 34. (Copy in Div. 50.)

The Arochlors, Application Data Bulletin No. P-115, pub. by Monsanto Chemical Co. of St. Louis, page 13. (Copy in Div. 64.) 

